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Gentisate-1,2-dioxygenase activity by an iron(II)-phenanthroline complex

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Abstract

In this work, we have synthesised and crystallographically characterized a mononuclear iron(II) complex, [\(\hbox {Fe}(\hbox {phen})_{3}\)](\(\hbox {NO}_{3})_{2}\cdot 2\hbox {H}_{2}\hbox {O}\) (1) (phen = 1,10-phenanthroline). Single crystal X-ray diffraction (SXRD) analysis revealed that 1 crystallizes in monoclinic system with P \(1^{-}\) space group. The lattice water molecules in 1 form a water-nitrate cluster, \((\hbox {H}_{2}\hbox {O})_{2}^{\ldots }(\hbox {NO}_{3})_{2}\) through strong H-bonding interaction mediated via iron(II) complex in a unique binding motif and provide additional stability to the compound in the solid state. This iron(II) complex is able to catalyze the cleavage of aromatic C-C linkage of 2,5-dihydroxybenzoic acid (Gentisic acid, GA) in oxygen environment. The iron(II) complex in the presence of two equivalent of triethylamine \((\hbox {Et}_{3}\hbox {N})\) binds with GA stoichiometrically in acetonitrile medium at \(25\,{^{\circ }}\hbox {C}\). Observation of GA-to-iron LMCT optical bands at 521 and 609 nm supports in situ generated iron-GA adduct in solution. This in situ generated iron-GA adduct reacts with molecular oxygen at the rate, \(k_{\mathrm{obs}} = 6.58 \times 10^{-3}\,\mathrm{min}^{-1}\) in acetonitrile and affords exclusively 2-oxo-4-hydroxy-hepta-3,5-dienedioic acid. The incorporation of both the oxygen atoms of molecular oxygen in the bio-mimicking activity of gentisate-1,2-dioxygenase by this iron(II)-phenanthroline complex remain a rare example in scientific literature.

Graphical Abstract

A mononuclear iron(II) phenanthroline complex exhibits significant catalytic activity towards oxidative cleavage of 2,5-dihydroxy benzoic acid at a rate, \(\hbox {k}_{\mathrm{obs}}(\mathrm{min}^{-1}) = 6.58\times 10^{-3}\) which predominantly produced 2-oxo-4-hydroxy-hepta-3,5-dienedioic acid upon addition of 2,5-dihydroxybenzoic acid in the presence of molecular oxygen.

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Acknowledgements

BB gratefully acknowledges the financial support by the Science & Engineering Research Board (SERB), Department of Science and Technology (DST), New Delhi, India under FAST TRACK SCHEME for YOUNG SCIENTIST (No. SB/FT/CS-088/2013 dtd. 21/05/2014).

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  1. Department of Chemistry, Raghunathpur College, Purulia, West Bengal, 723 133, India

    Abhranil De, Dhananjay Dey, Niranjan Kole & Bhaskar Biswas

  2. Department of Chemistry, Sidho-Kanho-Birsha University, Purulia, West Bengal, 723 104, India

    Ajit Das

  3. Department of Chemistry, Surendranath College, 24/2 M G Road, Kolkata, West Bengal, 700 009, India

    Bhaskar Biswas

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  1. Abhranil De
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De, A., Dey, D., Das, A. et al. Gentisate-1,2-dioxygenase activity by an iron(II)-phenanthroline complex. J Chem Sci 130, 26 (2018). https://doi.org/10.1007/s12039-018-1425-4

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